EP0411407B1 - Agent de couplage pour l'ensimage de fibres de verre - Google Patents

Agent de couplage pour l'ensimage de fibres de verre Download PDF

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Publication number
EP0411407B1
EP0411407B1 EP90113913A EP90113913A EP0411407B1 EP 0411407 B1 EP0411407 B1 EP 0411407B1 EP 90113913 A EP90113913 A EP 90113913A EP 90113913 A EP90113913 A EP 90113913A EP 0411407 B1 EP0411407 B1 EP 0411407B1
Authority
EP
European Patent Office
Prior art keywords
adhesion promoters
sizing
carbon atoms
glass fibres
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90113913A
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German (de)
English (en)
Other versions
EP0411407A2 (fr
EP0411407A3 (en
Inventor
Friedrich Dr. Jonas
Anna Dr. Marx
Alban Hennen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
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Publication of EP0411407A2 publication Critical patent/EP0411407A2/fr
Publication of EP0411407A3 publication Critical patent/EP0411407A3/de
Application granted granted Critical
Publication of EP0411407B1 publication Critical patent/EP0411407B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds

Definitions

  • the invention relates to new adhesion promoters for glass fiber coatings, coatings containing these adhesion promoters and glass fibers equipped therewith, and the use of the glass fibers coated in this way to reinforce plastics.
  • the glass fibers are sized, preferably with their Shaping during the fiber drawing process with a size that is compatible with the polymer to be reinforced and improves the adhesive properties of the glass fibers.
  • the properties of glass fiber reinforced plastics are significantly influenced by the performance of the fiber / plastic matrix interface.
  • the size means to ensure the manufacture and processing of the glass fibers.
  • the requirements are to be mentioned here e.g. with regard to cake flow, charging, protection against friction and glass breakage, as well as the sizes important for assembly, such as the bond, hardness and rigidity of the fiber strand.
  • the size is generally an aqueous solution or dispersion and usually consists, in terms of quantity, predominantly of one or more film formers and one or more adhesion promoters and, if appropriate, further additives such as, for example, lubricants, wetting agents or antistatic substances, etc. (see KL Loewenstein: The Manufacturing Technology of Continuous Glass Fibers, Elsevier Scientific Publishing Corp. Amsterdam, London, New York, 1973).
  • film-forming polymers are epoxy polymers, polyester polymers, polyurethanes, acrylic polymers, vinyl polymers, mixtures of such polymers and copolymers of corresponding monomers.
  • glass fiber sizes are used, the polyurethane dispersions as film formers and aminoalkyltrialkoxysilanes such as Contain aminopropyltriethoxysilane as an adhesion promoter (see K.L. Loewenstein 1.c.).
  • adhesion promoters include maleimimidopropyl trialkoxysilanes.
  • adhesion promoters according to the invention fulfill the stated task and do not have the above-mentioned disadvantages of the conventional adhesion promoters and lead to little or no yellowing with good mechanical properties at the same time.
  • the adhesion promoters according to the invention are compounds of the following formula I.
  • R represents an optionally branched alkylene radical with 1 to 20 C atoms or an arylene radical with 6 to 10 atoms optionally substituted with alkyl or halogen radicals
  • R1, R2, R3 are the same or different and represent an optionally branched alkyl radical having 1 to 20 C atoms or an aryl radical having 6 to 10 C atoms or hydrogen.
  • Adhesion promoters of the formula I in which R is one of the groups are preferred -CH2-CH2-, -CH2-CH2-CH2- or and R1, R2, R3 are the same or different and for H, -CH3, -C2H5 or stand.
  • adhesion promoters of the formula I are prepared by processes known per se, for example by reacting hydrazodicarbonamide II with amines of the formula III in which R, R1, R2, R3 have the meaning given above. These known methods are described, for example, in EP 45 371.
  • adhesion promoters according to the invention are used in sizing agents with which glass fibers are sized.
  • the normally aqueous sizing agents contain one or more film formers and, if appropriate, further additives such as lubricants, wetting agents and / or antistatic agents, etc.
  • Polyurethane dispersions are preferably used as film formers.
  • the size normally contains water or water / alcohol mixtures as solvents or dispersing agents.
  • the size there is also the possibility of applying the size from organic solvents to the glass fiber.
  • the size contains, based on the total amount, 1 to 20% of film former and adhesion promoter.
  • adhesion promoters of formula I according to the invention are preferably used in an amount of 0.1% to 2% based on the total amount of the size.
  • the size is applied to the glass fiber in a known manner, ie with the aid of suitable devices, such as spray or roller systems, onto the glass filaments drawn at high speed from spinnerets immediately after they have solidified.
  • suitable devices such as spray or roller systems
  • the sized, moist glass fibers are dried at temperatures of 90-150 ° C. Drying is not only to be understood to mean the removal of water and other volatile constituents, but also, for example, the setting of the sizing constituents. Only after the drying process has been completed has the size changed into the finished coating compound.
  • the glass fibers so sized are processed in plastics, preferably polyamides.
  • the size is applied in the manufacture of the glass fiber as follows: After emerging from the spinneret (bushing), the filaments are drawn by rapid removal and pass through a size applicator in which the aqueous binder is located.
  • This applicator consists of a roller system, the foremost roller of which is treated with size. The filaments are guided past this roller and take up the aqueous size. The wet cakes are then dried in a convection oven.
  • the glass fibers (E-glass) sized in this way and dried for 9 h at 130 ° C. are in the form of strands cut to a length of 6 mm, each consisting of 1000 individual threads with a diameter of 10 ⁇ , in a twin-screw extruder in polyamide 6 (Durethan B 31F, Bayer AG), the glass content in the glass fiber reinforced polyamide being 30%.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (6)

  1. Agents d'accrochage de formule générale I
    Figure imgb0016
     dans laquelle
    R   représente un reste alkylène éventuellement ramifié ayant 1 à 20 atomes de carbone ou un reste arylène de 6 à 10 atomes de carbone substitués le cas échéant avec des restes alkyle ou halogéno
    et
    R¹, R², R³   sont identiques ou différents et représentent un reste alkyle éventuellement ramifié ayant 1 à 20 atomes de carbone, un reste aryle ayant 6 à 10 atomes de carbone ou de l'hydrogène.
  2. Agents d'accrochage suivant la revendication 1, dans lesquels
    R   représente un groupe -CH₂-CH₂-, -CH₂-CH₂-CH₂- ou
    Figure imgb0017
    et R¹, R², R³   sont identiques ou différents et représentent
       H, -CH₃, -C₂H₅,
    Figure imgb0018
  3. Procédé de production des agents d'accrochage suivant l'une des revendications 1 et 2 par réaction d'hydrazodicarboxamide de formule II avec des amines de formule III, avec élimination d'ammoniac, R ayant la définition mentionnée dans la revendication 1 ou 2
    Figure imgb0019
  4. Utilisation des agents d'accrochage suivant l'une des revendications 1 et 2 dans des compositions d'ensimage.
  5. Utilisation des compositions d'ensimage suivant la revendication 4 pour l'ensimage de fibres de verre.
  6. Utilisation des fibres de verre ensimées suivant la revendication 5 pour le renforcement de matières plastiques, notamment de polyamides.
EP90113913A 1989-08-02 1990-07-20 Agent de couplage pour l'ensimage de fibres de verre Expired - Lifetime EP0411407B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3925523 1989-08-02
DE3925523 1989-08-02

Publications (3)

Publication Number Publication Date
EP0411407A2 EP0411407A2 (fr) 1991-02-06
EP0411407A3 EP0411407A3 (en) 1991-07-24
EP0411407B1 true EP0411407B1 (fr) 1994-03-02

Family

ID=6386330

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90113913A Expired - Lifetime EP0411407B1 (fr) 1989-08-02 1990-07-20 Agent de couplage pour l'ensimage de fibres de verre

Country Status (2)

Country Link
EP (1) EP0411407B1 (fr)
DE (1) DE59004745D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10333941A1 (de) * 2003-07-25 2005-02-17 Johns Manville Europe Gmbh Schlichte zur Behandlung von Glasfasern sowie mit diesen Schlichten ausgerüstete Glasfasern
EP2666922B1 (fr) 2012-05-23 2015-07-22 Groz-Beckert KG Composant en béton avec renfort textile

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH641470A5 (de) * 1978-08-30 1984-02-29 Ciba Geigy Ag Imidgruppen enthaltende silane.
JPH0637609B2 (ja) * 1986-01-24 1994-05-18 マサチユ−セツツ インスチチユ−ト オブ テクノロジ− 接着促進剤

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10333941A1 (de) * 2003-07-25 2005-02-17 Johns Manville Europe Gmbh Schlichte zur Behandlung von Glasfasern sowie mit diesen Schlichten ausgerüstete Glasfasern
EP2666922B1 (fr) 2012-05-23 2015-07-22 Groz-Beckert KG Composant en béton avec renfort textile
US9663950B2 (en) 2012-05-23 2017-05-30 Groz-Beckert Kg Textile-reinforced concrete component

Also Published As

Publication number Publication date
DE59004745D1 (de) 1994-04-07
EP0411407A2 (fr) 1991-02-06
EP0411407A3 (en) 1991-07-24

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